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Biochem Soc Trans. 2005 Feb;33(Pt 1):3-6.

Electrocatalytic proton reduction by dithiolate-bridged diiron carbonyl complexes: a connection to the H-cluster?

Author information

1
School of Chemistry, University of Melbourne, Victoria 3010, Australia.

Abstract

Spectroscopic and electrochemical investigation of electrocatalytic proton reduction by Fe(2)(mu-pdt)(CO)(6), 1, have been interpreted in terms of a reaction scheme involving sequential electron-proton reactions to give a two-electron, two-proton product that undergoes rate-limiting dihydrogen elimination. Further reduction, at slightly higher negative potentials, gives a more reactive product and this process dominates reactions conducted at higher acid concentrations. Inhibition of the electrocatalytic reaction by CO is due to the more efficient loss of catalyst and this is best modelled by a reaction that is second order in terms of 1(-). During electrocatalytic proton reduction a new species is observed, which features a bridging CO group and the wavenumbers of the nu(CO) modes of the terminally bound carbonyl groups are similar to those of the carbonyl groups bound to the oxidized form of the H-cluster.

PMID:
15667249
DOI:
10.1042/BST0330003
[Indexed for MEDLINE]

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